AU641758B2

AU641758B2 - Macrocyclic ligands bonded to a maxtrix and their use in selectively and quantitatively removing and concentrating ions present at low concentrations from mixtures thereof with other ions

Info

Publication number: AU641758B2
Application number: AU76090/91A
Authority: AU
Inventors: Jerald S. Bradshaw; Ronald L. Bruening; James J. Christensen; Reed M. Izatt
Original assignee: Brigham Young University
Current assignee: Brigham Young University
Priority date: 1987-09-04
Filing date: 1991-04-29
Publication date: 1993-09-30
Anticipated expiration: 2008-08-29
Also published as: DE3872628T2; AU2164288A; IL86766A; AU606240B2; DE3872628D1; EP0306334B1; JP2736256B2; JPH01139142A; IL86766A0; EP0306334A3; AU2704188A; EP0306334A2; AU7609091A

Description

641758 S F Ref: 8183601 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: Name and Address of Applicant: 0 Brigham Young University Provo Utah 84602 UNITED STATES OF AMERICA Jerald S. Bradshaw, Ronald and James J. Christensen Actual Inventor(s): Address for Service: L. Bruening, Reed M. Izatt Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Males, 2000, Australia Complete Specification for the invention entitled: Macrocyclic Ligands Bonded to a Maxtrix and their use in Selectively and Quantitatively Removing and Concentrating Ions Present at Low Concentrations from Mixtures thereof with other Ions The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/4 S-

ABSTRACT

The invention has composition of matter and process aspects. The composition of matter aspect relates to certain macrocyclic compounds which have at least four -A-CH 2

-CH

2 groups in which A is selected from

-OCH

2

-S-CH

2 -NR- and -N(R)CH 2 in which R is selected from H, lower alkyl and benzyl and the hydrocarbon chain has an end group

X

-Si-O-Matrix in which X is selected from lower alkyl, benzyl, phenyl,

X

halogen, OCH 3

OC

2

H

5 and 0-Matrix and Matrix is selected from glass, glass fibers, titania, zirconia, alumina and nickel oxide.

Representative families of compounds contemplated by the present invention are illustrated by the four structural formulae below: o 9 g 9 So...

.a r

A

N D ND~- F BX E C -CI CH 2 Si-0-Matrix i.

X

F

x

CH

2 0 (C

H

2 3 -Si-O-Matrix

X

A-F a any combination of 0 or S or NR (R H or any alkyl or benzyl); n 0 to 4; X any alkyl or C1 or O-Matrix (Generic) A-F 0; n 0 to 2; X CH 3 or C1 or 0-Matrix (Species) A, C, D, F 0; B and E N-R (R H or alkyl or benzyl); n 0 to 2; X CH 3 or Cl or O-Matrix (Species) A-F a any combination of 0 or S or NR (R H or any alkyl or benzyl); 1, m, n 0 to 2; X any alkyl or Cl or 0-Matrix (Generic) A-F 0; 1 m n 1; X CH 3 or C1 or 0-Matrix (Species) LMM/KXW:1344y 2x 0 CH) -Si-0-Matrix X

R

N N K) H (H2 3 -Si-O-Matrix 0 0- H~ 0C0 o 0 n -0 to 2; X -CH 3 or Cl or n=-0 to 2; R =any al kyl X =CH 3 or 0-Matrix Cl or 0-Matrix The process aspect involves the use of any of these compounds packed in a column through which a solution of the multiple ions is flowed to complex with the compound and separate a desired selected ion from a multiple ion solution, breaking the complex by flowing a receiving liquid through the column to free the desired ion and recovering the freed desired ion from the receiving liquid.

*Soo 4 0 000 000000 4 0050 00 9 *000

S

*0oe @000 00 .9 0 00 0 9 0.

0 00 LMM/KXW:l 344y This invention is directed to a single improvement in or modification of the invention described and claimed in Australian Patent No. 606240.

The present invention comprises a composition of matter and a process of using it.

The composition of matter comprises a matrix, glass, glass fibers, titania, zirconia, alumina and nickel oxide, having a covalent bond to certain macrocyclic compounds through a hydrocarbon chain with or without an ether oxygen linkage. These certain macrocyclic compounds have at least four -A-CH 2

-CH

2 groups in which A is selected from -OCH 2

-SCH

X

-Si-O- Matrix in which X is selected from lower alkyl, benzyl, phenyl, halogen,

I

X

OCH

3

OC

2

H

5 and O-Matrix and Matrix is selected from glass, glass fibers, titania, zirconia, alumina and nickel oxide.

Representative families of compounds contemplated by the present invention are illustrated by the four structural formulae below:

CA-

F

C

E

ID

S,

soot 0 05 5 *SeS *r 9005

S

55 *5 a) A-F any combination of 0 or S or N-R (R H or any alkyl or benzyl); n O to 4; X any alkyl or Cl or O-Matrix (Generic) b) A-F O; n O to 2; X CH3 or C1 or O-Matrix (Species 1) c) A, C, D, F O; B and E N-R (R H or alkyl or benzyl); n O to 2; X CH 3 or C1 or O-Matrix (Species 2) a) A-F any combination of O or S or N-R (R H or any alkyl or benzyl); m, n O to 2; X any alkyl or C1 or O-Matrix (Generic) b) A-F 0; 1 m n 1; X

CH

3 or C1 or O-Matrix (Species) 3 of 1 r 4

CCH

2 3 -Si-O-Matrix N- N 0 0 n 0 to 2; X CH 3 or C1 or n 0 to 2; R any alkyl; X 0-Matrix CH 3 or C1 or 0-matrix S3 j in which matrix is selected from glass, glass fibers, titania, zirconia, alumina and nickel oxide.

The process comprises selectively and quantitatively removing and concentrating a selected ion or group of ions present at low concentrations from a plurality of other ions in a multiple ion solution in which the other ions may be present at much higher concentrations by bringing the multiple ion solution into contact with a compound of the invention. The preferred embodiment disclosed herein involves carrying out the process by bringing a large volume of the multiple ion solution into contact with a compound of the invention in a separation column through which the mixture 1 5 is first flowed to complex the desired ion or ions with said compound followed by the flow through the column of a small volume of a receiving liquid to break the complex by chemical or thermal means, dissolve the desired ions and carry them out of the column. Other equivalent apparatus may be used instead of a column, a slurry which is filtered, washed 2. with a receiving liquid to break the complex and recover the desired ion.

The desired metal ions are then recovered from the receiving phase by well known procedures.

More particularly, the process comprises forming a chemical covalent bond between the matrix and at least one of the compounds, placing the resulting bonded matrix in a contacting device such as a tall column, LMM/KXW:1344y i 5 causing a large volume of the mixture of ions to flow through the column where the desired ions complex with the bonded matrix which separates them from the rest of the mixture which flows out of the column, then flowing a small volume of the receiving liquid through the column to break the complex and dissolve and carry out of the column the desired ion(s). The desired metal ions are then recovered from the receiving phase by well known procedures.

BACKGROUND OF THE INVENTION The fact is known that macrocyclic polyethers and other macrocyclic ligands present as solutes in a solvent such as water are characterized by their ability to selectively form strong bonds with particular ions or groups of ions present as solutes in the same solvent according to size, donor atom-related and other well known selectivity rules as noted in articles by R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D. Lamb, 3.J.

Christensen, and D. San, THERMODYNAMIC AND KINETIC DATA FOR CATION- MACROCYCLE INTERACTION, Chem. Rev., 1985, Vol. 23, 271-339 and by L.F.

Lindoy, in PROGRESS IN MACROCYCLIC CHEMISTRY, edited by R.M. Izatt and 3.J.

Christensen, JOHN WILEY SONS, pages 53-92 (1987). However, researchers have not previously been able to incorporate macrocycles into separation systems where the behavior of the macrocycle in the separation system in comparison to that of the macrocycle as a solute is unchanged and/or the macrocycle will remain in the separation system. Articles such as those entitled ION-CHROMATOGRAPHIC SEPARATION OF SILICA CRAFTED WITH BENZO-18- CRONN-6 ETHER by M. Lauthard and Ph. Germain, J. Liquid Chromatogr, 1985, Vol. 8, 2403-2415, and ION-CHROMATOGRM.HY ON POLY (CRONN ETHER-MODIFIED) SILICA POSSESSING HIGH AFFINITY FOR SODIUM by M. Naksjima, K. Kumura, E.

Hayata, and T. Shono, J. Liquid Chromatogr. 1984, Vol. 7, 2115-2125, have disclosed the bonding of crown ethers to silica gels but they and most other reported macrocycle bonded silicas contain a benzene group or other 0."30 electron withdrawing groups as part of a macrocycle side chain which reduces the ability of the macrocycle to bond with ions in comparison to the situation where the macrocycle and ions are present as solutes in solution. The only other reported examples of bonding of macrocycles to sand or silica gel have involved bonding via a side chain connected to one of the electron rich macrocycle donor atoms, nitrogen. One such reference is entitled AN OXYGEN-NITROGEN DONOR MACROCYCLE IMMOBILIZED ON LMM/KXW:1344y 6 SILICA GEL, A REAGENT SHOWING HIGH SELECTIVITY FOR Cu(II) IN THE PRESENCE OF Co(II). Ni(II) OR Zn(II), by V. Dudler, L.F. Lindoy, D. Sallin and C.W.

Schlaepfer, Aust. J. Chem., submitted for publication. However, such bonding changes the geometry of the compound and greatly reduces the ability of the macrocycle to interact with ions. Prior researchers in this field confined their research to analytical chromatographic applications and disclosed no concept of industrial separation applications where strong macrocycle-lon bonding is required to quantitatively recover the desired ion(s) from solution and high selectivity is required to obtain a product free from contaminants. The strength of macrocycle-ion bonding is particularly important when ions present in solution at low concentrations need to be recovered. The greater the value of the equilibrium constant for ion-macrocycle interaction, the lower the initial concentration of the ion in solution can be and still be efficiently and quantitatively i5 complexed. Hence, the ability to attach these macrocycles to sand or silica gel or other matrixes without reducing the ability of the macrocycle to complex ions is of the utmost importance in the industrial use of macrocycles. The process of the present invention successfully accomplishes this feat.

SUMMARY OF THE INVENTION The compounds of the present invention comprise certain macrocyclic ligands having a hydrocarbon side chain that is covalently bonded to a matrix selected from glass, glass fibers, titania, zirconia, alumina and nickel oxide. These certain macrocyclic compounds have at least four

-A-CH

2

-CH

2 groups in which A is selected from -OCH 2

-SCH

2 -NR- and -N(R)CH 2 in which R is selected from H, lower alkyl and benzyl. The hydrocarbon side chain has an end group -Si-O- covalently bonded to the Matrix in which X is selected from lower

X

alkyl, benzyl, phenyl, halogen, -OCH 3

OC

2

H

5 and 0-Matrix.

According to a first embodiment of the present invention there is provided a process of separating one or more selected species of ions from a solution containing said ions, said process comprising contacting the solution with a composition of matter comprising a hydrocarbon chain covalently bonded to a macrocyclic compound, wherein the LMM/KXW:1344y 7macrocyclic compound has at least four -A-CH 2

-CH

2 groups in which A is selected from 0, OCH 2 S, SCH 2 NR, and NRCH 2 with R being selected from hydrogen, alkyl and benzyl, and wherein the hydrocarbon chain has an end group

X

-Si---Matrix, in which X is selected from alkyl, benzyl, phenyl, halogen,

OCH

3

,.OC

2

H

5 and 0-Matrix, and with Matrix being selected from glass, glass fibers, titeiia, zirconia, alumina and nickel oxide; and forming a complex between said selected species of ions and said composition of matter to remove said selected species of ions from the solution.

According to a second embodiment of the present invention there is provided a composition of matter selected from 4 0 0 0000 000 4 04i 00 0 s 0040 4 0t 0 6000

S.

S

044 r A F B E CH 20 (C 3-Si-O-Matri x

D

I

(CH2 3-Si--Matrix

X

*o q.

0 04 0 04 0 0 LMM/KXW:1344y -8-

X

O CH 2 3 -Si-O-Matrix

X

N

0 0 n

R

N N i o- cH2°cCB:2) 3- i-O-Matrix QOO O 0o0 NR NR 0 0 S. CH20 (CH 2) 3-S i 0 Mat rix 2 2 3x wherein A through F are any combination of 0 or S or NR; X is alkyl or chlorine or 0-Matrix; Matrix is selected from glass, glass fibers, titania, zirconia, alumina and nickel oxide; m, n and 1 are each integers from 0 to 2; and p is an integer from 0 to 4.

LMM/KXW:1344y 9 According to a third embodiment of the present Invention there is provided a composition of matter comprising a macrocyclic compound having at least four -A-CH 2

-CH

2 groups wherein A is a member selected from 0,

OCH

2 S, SH 2 NR and NRCH 2 with R being a member selected from hydrogen, alkyl and benzyl; and a hydrocarbon chain covalently bonded to said macrocyclic compound, with the hydrocarbon chain having an end group

X

I

-Si-0-Matrix in which X is selected from alkyl, benzyl, phenyl, halogen,

OCH

3

OC

2

H

Representative families of compounds contemplated by the present invention are illustrated by the four structural formulae on pages 1 and 2. The process of the present invention uses the compounds, which are characterized by high selectivity for and removal of desired metal ions or groups of metal ions present at low concentrations from the source phase containing a mixture of metal ions with the ions one does not desire to remove present in much greater concentrations in the solution, in a separation device such as a column through which the solution is flowed.

The process of selectively removing and concentrating the desired ion(s) is characterized by the ability to quantitatively complex from a large volume of solution the desired ion(s) when they are present at low concentrations. The said ions are recovered from the separation column by flowing through it a small volume of a receiving phase which contains a solubilized reagent which need not be selective, but which will strip ions from the macrocyclic ligand quantitatively. The recovery of the desired metal ions from the receiving phase is easily accomplished by well known procedures.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described and illustrated by reference to the drawings in which: Fig. 1 represents schematically a suitable column for holding the matrix macrocyclic ligand (crown) material through which a solution of metal ions can be flowed to complex selectively with a desired ion or group of ions in accordance with the invention.

LMM/KXW:1344y 10 Figs. 2 to 5 represent the group of families of neutral macrocyclic ligands covalently bonded to matrix comprising the compounds of the invention, and Fig. 6 represents a graph of the predicted (o ,oints) and actual (curve) remaining amount of Sr 2 in a solution Initially containing 1 M MgC1 2 and 0.001 M SrCI 2 after flowing the solution through an 18-crown-6-bonded matrix column .v the amount of volume of the solution which has been passed through the column. The analytical detection limit is listed for those experimental points where no Sr 2 could be detected.

DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION PREPARATION OF MATERIALS Macrocycles which do not contain electron withdrawing groups and which are capable of being bonded to the matrix must be synthesized. Then the macrocycle must be covalently bonded to the matrix.

EXAMPLE 1 One method of preparing the compounds of Fig. 2, is to react the allyloxy forms of the crowns with triethoxysilane or chlorodimethylsilane or dichloromethylsilane followed by heating the resulting silane with a matrix as follows: 0 0 O O CH 2CH2CH=CH 1) HSi(OC 2 H5 3+Pt cat 2)Matrix+ heat C* 0 0 0 *O X o 0 CH20 (CH2) 3 i-0-Matrix 0

X

n n 0 or 1 or 2 X CH 3 or C1 or alkoxy or 0-matrix The synthesis of thie allyloxy forms of the crowns, which is not part of the present invention, is described in an article entitled FACILE LMM/KXW:1344y -11- SYNTHESIS OF HYDROXYMETHYLCRONN ETHERS by I. Ikeda, H.E. Mura and M.

.0kahara, Synthesis pages 73 and 74 (1984), which is incorporated herein by reference.

EXAMPLE 2 A method for preparing the macrocyclic compounds of Fig. 3 is to react the cryptand compound having a -CH 2

-O-CH

2

CH=CH

2 side chain with triethoxysilane or trichlorosilane or chlorodimethylsilane or dichloromethylsilane in the presence of a platinum catalyst and heating this compound with matrix as follows: 1 0 0 0 0

N

o lH. OCH CH=CH .2 2 2. 2 3 G Jog 0 4 0 e 1) HSi(OC 2 5 3 Pt cat 2) Matrix +theat

X

*a m 0 oro or 2 04 4 CH O(CH -Si-O-Matrix 1 0 or 1 or 2 m 0 or I or 2 n 0 or 1 or 2 X CH 3 or Cl or alkoxy or O-Matrix LMM/KXW:1344y

I-

-12 The synthesis of the -CH 2 CH 2 CH-CH 2 substituted 2.2.2 cryptand (I n 1) which is not part of the present invention, is described in an article entitled SYNTHESIS OF HYDROXYMETHYL FUNCTIONALIZED DIAZACROWNS AND CRYPTANDS by David A. Babb, Bronislaw P. Czech and Richard A. Bartsch, J. Heterocy~1ic Chem., Vol. 23, pages 609-613 (1986), which is incorporated herein by reference.

EXAMPLE 3 A method of preparing the macrocyclic compounds of Fig. 4, is to react 4-allyloxypyrldino-18-crown-6 with triethoxysilane or trichiorosilane or chiorodimethylsilane or dichioromethylsilane and heating the resulting silane and matrix as follows: OCH 2CH=CH2 2N BC B0 C, 0 as C C 0.

0 ~0) IP ceat LMM/KXW: 1344y S- 13 X x S0(CH) 3 -Si-0-Matrix O O 0 0 0 0 0 n n 0 to 2, X CH 3 or Cl or 0-Matrix o* 0* 5 The synthesis of 4-allyloxypyridino-18-crown-6 (where n which is not part of the present invention, is described in an article entitled PROTON-IONIZABLE CROWN ETHERS, 3. SYNTHESIS AND STRUCTURAL STUDIES OF MACROCYCLIC POLYETHER LIGANDS CONTAINING A 4-PYRIDINE SUBCYCLIC UNIT, by Jerald S. Bradshaw, Yohji Nakatsuji, Peter Huszthy, Bruce E. Wilson, N.

Kent Dalley and Reed M. Izatt, 3. Heterocyclic Chem. Vol. 23, pages 353-360 (1986), which is incorporated herein by reference.

It should be emphasized that any macrocycle which can be synthesized r with a -CH -0-CH 2 CH=CH side chain or the like attached to one of the regular carbon atoms of the macrocycle could then be covalently bonded to i5 the matrix. The interaction properties of this bonded .macrocycle will not differ from those of the unsubstituted macrocycle present as a solute in solution when such a macrocycle does not contain electron withdrawing substituent groups and the bonding to the matrix does not occur via one of the macrocycle donor atoms. This will now be described in more detail in the following description of the metal ion recovery and concentration process.

METAL ION RECOVERY AND CONCENTRATION PROCESS The metal ion recovery and concentration process of the invention relates to the selective recovery of desired metal ions from mixtures LMM/KXW:1344y 14 thereof with other metal ions using the compounds of the invention as defined above. Effective methods of recovery and/or separation of metal ions, particularly silver, lead, cadmium, and other heavy metals, from one another in culinary water supplies, waste solutions, deposits and industrial solutions and silver recovery from waste solutions, from emulsions on photographic and X-ray film, represent a real need in modern technology. These ions are typically present at low concentrations in solutions containing other ions at much greater concentrations. Hence, there is a real need for a process to selectively recover and concentrate these hazardous and/or desirable ions. The present invention accomplishes this separation effectively and efficiently by the use of compounds selected from the families represented by Figs. 2 to The process first involves selecting a macrocycle-bonded matrix where the particular macrocycle will selectively complex the ion(s) of interest.

J5 There is a large data base for measurements of macrocycle-ion interactions where the macrocycle is unsubstituted and present as a solute in a solvent. Much of this data base is presented in an article by R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D. Lamb, 3.J. Christensen, and D. Sen, THERMODYNAMIC AND KINETIC DATA FOR CATION-MACROCYCLE INTERACTION, Chem.

Rev. Vol. 23, 271-339 (1985). Previously, this data base has only provided general qualitative predictions about the behaviour of macrocycles incorporated into separation processes. However, in the process of the invention the equilibrium constants for lon-macrocycle interaction for macrocycles present as solutes in solution vs. that for macrocycles bonded to a matrix show little or no variation. Data comparing the interaction of several ions with both types of the macrocycle 18-crown-6 are given as an example of this point in Table 1. It is emphasized that similar interaction with metal ions of the bonded macrocycle and macrocycle in solution is only obtained when electron withdrawing groups are not attached 3B0 to the macrocycle and when the macrocycle is not attached to the matrix via one of the donor atoms of the macrocycle.

The data base for macrocycle-cation interaction can be used in choosing a macrocycle for recovering a particular cation. The selective removal and Table 1.

LMM/KXW:1344y 15 Comparison of Aqueous Equilibrium Constants for 1:1 Cation-18-Crown-6 Interaction with the Macrocycle Free in Solution vs. being Bound to the Matrix Log Ka Free Bound Cation Macrocycle Macrocycle Sr 2 2.72 2.6 b Tl+ 2.27 2.2 Ba 2 3.87 3.7b Pb 2 4.27 4 .0 c Ni 2 0 0.

2 b go d aLog K values for the free macrocycle, which are not part of the present 6 S invention, are taken from R.M. Izatt, J.S. Bradshaw, S.A. Nielsen, J.D.

6 al Lamb, J.J. Christensen, and D. Sen, THERMODYNAMIC AND KINETIC DATA FOR CATION-MACROCYCLE INTERACTION, Chem. Rev., Vol. 85, 271-339 (1985). Log K values for the bound macrocycle where determined by us.

bionic strength 3 M.

Clonic strength 1 M.

recovery of Pb 2 and Ba 2 from aqueous solutions using 18-crown-6 i 4. bounded to a matrix are examples of a suitable choice of macrocycle for a specific need. The data base measurements indicate that Pb 2 and Ba 2 als are selectively complexed by 18-crown-6 by at least an order of magnitude over all other cations. The selectively over cations often present in large excess Na Mg 2 Ca 2 is much greater. The S equilibrium constant values in Table 1 confirm the suitability of the 9 o choice of 18-crown-6 as an appropriate macrocycle for the task. The 18-crown-6 bonded matrix has been tested for its ability to remove Pb 2 from H 2 0. These data are present in Table 2. The dimensions TABLE 2.

LMM/KXW:1344y 16 The Reduction of Pb 2 Concentrations in Aqueous Solution Using an 18-Crown-6 Bonded Matrix Columna Initial Pb 2 Final Pb 2 Volume of Pb 2 Concentration Concentration Solution ippm) (ppb) (ml) 207 b 30 c d <30c >250 20 e 30 C 100 aThe cylindrical column used was 1.90 cm In diameter and contained a cm height of the material. The capacity was 5.3 moles of macrocycle/m 3 matrix.

bMg 2 was also present at a concentration of 1 Molar.

c C30 ppb is the detection liiit of the atomic absorption spectrophotometer.

M g 2 and Ca 2 were also present at 0.6 and 0.003 Molar, respectively.

eMg2+ was also present at 0.7 Molar.

and capacity of the small column used are given as footnotes to the table.

The data in Table 2 shows that great reductions in aqueous Pb 2 concentrations can be achieved using the 18-crown-6 bonded matrix column even when another cation is present in solution at much greater concentrations. The matrix can interact with ions to some degree in and of itself. However, tests using a plain matrix column under conditions identical to those performed with macrocycle bonded matrix showed that the aqueous stream Pb 2 concentration reductions were not as great. In particular, the plain matrix column performed quite poorly under conditions where cations other than ?b 2 were present at much greater concentrations than that of Pb 2 The effect of the matrix interaction with ions flowing through the column can be minimized by blocking the majority of the -OH sites present with trimethylsilyl groups.

*9 The same 18-crown-6 bonded mat'six column has also been tested for its ability to selectively remove Sr 2 from a solution containing 1 M MgCl 2 and 0.001 M SrC1 2 The molar concentrations of Sr 2 in the aqueous stream coming out of the bottom of the column vs. the corresponding volumes of solution which have been flowed through the column are plotted as the exponential points in Fig. 6. A predicted Sr 2 concentration vs. volume LMM/KXW:1344y 17 plot is also shown(solid line). The predicted plot was obtained by numerically solving the partial differential mass balance equation for the column using the equilibrium constant for Sr 2 +-macrocycle interaction.

Similar tests with matrix columns which did not contain the bonded macrocycle showed that very little Sr 2 could be removed from the aqueous source phase.

Once the desired ion(s) are attached to the macrocycle bonded matrix column they must be removed using a small volume of a receiving phase so that a concentrated and purified product is obtained. In the Pb 2 and Sr 2 recovery tests described, 99% of the purified Pb 2 or Sr 2 was recovered from the column using 25 ml of a concentrated basic solution of either ethylenediamine tetraacetate(EDTA), citrate, or acetate. These reagents from stronger complexes with the ion(s) than the macrocycle does.

Hence, they can effectively strip ion(s) from the macrocycle. These .0,J5 ion-receiving phase reagent complexes are easily broken by adding acid to 00 e the solution. These species can be recovered as a solid if desired. For 2+ example, the Pb can be recovered as a solid by using H 2

SO

4 as the acid and, hence, precipitating PbSO 4 An example of the use of these materials and processes is the quantitative and selective removal of undesired heavy metals such as Pb 2 from blood. The matrix bonded macrocycle 18-crown-6(Fig 2. A F oxygen, n 1) selectively complexes Pb 2 over Na+, Ca 2 Fe 3 proteins and other materials necessary in the body by at least 2 orders of magnitude.

Although the invention has been described and illustrated by ,,ga reference to certain specific macrocycle ligands and processes of using them, analogs of these macrocycles are within the scope of the compounds and processes of the invention as defined in the following claims.

IJ 0 0 St LMM/KXW:1344y

Claims

1. A process of separating one or more selected species of ions from a solution containing said ions, said process comprising contacting the solution with a composition of matter comprising a hydrocarbon chain covalently bonded to a macrocyclic compound, wherein the macrocyclic compound has at least four -A-CH 2 -CH 2 groups in which A is selected from 0, OCH 2 S, SCH 2 NR, and NRCH 2 with R being selected from hydrogen, alkyl and benzyl, and wherein the hydrocarbon chain has an end group X Si-0-Matrix, in which X is selected from alkyl, benzyl, phenyl, S halogen, OCH 3 OC 2 H 5 and 0-Matrix, and with Matrix being selected from glass, glass fibe.s, titania, zirconia, alumina and nickel oxide; and forming a complex between said selected species of ions and said composition of matter to remove said selected species of ions from the solution.

2. A process according to claim 1 further comprising the steps of separating said solution, from which the selected ions have been removed, from the complex; and contacting the complex with an eluant which frees the selected ions from the complex into solution in the eluant.

3. A process according to claim 1 or claim 2, wherein said composition of matter is selected from *000 C CH 2OCCH2 3-Si-O-Matrix "F B P LMM/KXW:1344y 19 x x O (CU 2 3 -Si-O-Matrix o~* Go., 09G0 S S *0 0 *S0. 0 0 9 ft. 5 0000 S. 0e **0 0 0 N NI-,R N S. OS 0 S* S So S 4 0 OS 0 0 x CU~ (C 2 3 -Si--Mt 0O x 0 \,vnJ LMM/KXW: 1344y 1 20 0 0 NR NR x CH 2 OCCH) 3 -Si-O-Matrix X wherein A through F are any combination of 0 or S or NR; X is alkyl or chlorine or 0-Matrix; Matrix is selected from glass, glass fibers, titania, e* zirconic, alumina and nickel oxide; m, n and 1 are each integers from 0 to 2; and p is an Integer from 0 to 4. b a 4. A process according to claim 3, wherein said composition of matter is 0 0 in which X is methyl or chlorine or I-Matrix. matter is NR CH20 CCH 2 3-Si-O-Matrix in which X is methyl or chlorine or 0-Matrix. A process according to claim 3, wherein said composition of matter is 0 NR O XX in which X is methyl or chlorine or 0-Matrix. LMM/KXW:1344y

6. matter is 21 A process according to claim 3, wherein said composition of A B N C D N x CHO (CCH 2 3 -Si-O-Matrix X A process according to claim 3, wherein said composition of o x CH 2 (CH -Si-O-Matrix 20 CCH 2 3- X s 60o0

7. matter is S 0. me a egg *o* 90 e in which X is methyl or chlorine or 0-Matrix.

8. A process according to claim 3, wherein said composition of matter is x. O (CH2 3 -Si-O-Matrix x 0 0 O O in which X is methyl or chlorine or 0-Matrix. LMM/KXW:1344y

9. .matter is 22 A process according to clai1m 3, wherein said compoSition of N N o (CH2 3 i-O-Matrix I-.I 0 x 0 0 (0 x is alkyl and X is methyl or chlorine or 0-Marrix. A composition of matter selected from o a 00.l see* ebbe lb a *a a a a ow in which R

10. KAlh F E D D\ B x .11 C CH 0 (CH 3 Si-O-Matrix j 2 x3-1 too**: a :05 S a 00 lb a. @0 lb a a 00

14-\ A B 1J N '"MN CH O(CE 2 3 -Si-o-matri'. x LMM/KXW:1344y 23 X o 2 3 Si-O-Matriz X <N 6 0 0 0 n N goo CH 20(CH 3 1 @*00 4 J 0* ass. 0 CH 2 )-Si-atr-Mati AN 0 X wherein A through F are any combination of 0 or S or NR: X is alkyl or chlorine or 0-Matrix; Matrix is selected from glass, glass fibers, titania, zirconia, alumina and nickel oxide; m, n and I are each integers fromt 0 to 2; and p is an integer from 0 to 4. a sept Ca aoo NR NR cas~QCu 2 -s--4t' wherein A through F are any combination of 0 or S or NR: X is alkyl or chlorine or 0-Matrix; Matrix is selected from glass, glass fibers, titania, z~irconia, alumina and nickel oxide; m, n and 1 are each integers from 0 to 2; and p is an integer f:-om 0 to 4. LMM/KXW:1344y 24 11. A composition of matter according to claim 10 represented by the .structural formula F B C CK20 (C2) Si-O-Matrix D x S 0*9 12. A composition according to claim 10 represented by the structural formula 0 "0 0 X 0 0 CHO (CH 2 3-S i--atr i x k^°\y a P NR 0 C20 CH2 3-Si-O-Matric in which X is methyl or chlorine or 0-Matrix and p is an integer from 0 to 2. 13. A composition of matter according to claim 10 represented by the structural formula .0 MR NR CH- OCCH -Si-O-Mat-i.C in which X is methyl or chlorine or 0-Matrix and p is an integer from 0 to 2. LMM/KXW:1344y 25 14. A composition of matter according to claim 10 represented by the structural formula F A N E~ CHO (CCH 2 3-Si-O-Matrix X

15. A composition of matter according to claim 10 represented by the structural formula to.. 0 0 00 I 0 0 a 6 x X in which X is methyl or chlorine or 0-Matrix.

16. A composition of matter according to claim 10 represented by the structural formula 0 CH 2 3 Si-o-Matrix CC I r M 0 0 0 in which X is methyl or chlorine or 0-Matrix. LMM/KXN:1344y 26

17. A composition of matter according to claim 10 represented by the .structural formula RN N N rCHOC CH 2 3 -Si-O-Matri x o 0x is alkyl and X is methyl or chlorine or 0-Matrix. A composition of matter according to claim 10 represented by the formula 0 o o iB ces *o a re 9 0O 0. in which R

18. structural 000 <rr CEo (CE 2 3 -Si-O-Matrix x wherein X is methyl or chlorine or 0-Matrix.

19. A composition of matter according to claim 10 represented by the structural formula H Oi/ O N 0 0 x t Cato CLI2J 32 i-0-Y--at=_JzC x wherein X is methyl or chlorine or 0-Matrix and 1 is an integer from 0 to 2. LMM/KXW:1344y 27 A process of separating a selected ion from a plurality of other ions in a multiple ion solution, substantially as hereinbefore described with reference to any one of the Examples or Fig. 1.

21. A composition of matter comprising matrix covalently bonded to a macrocycle compound, as hereinbefore described with reference to any one of the Examples or any one of Figs. 1 to

22. A composition of matter comprising a macrocycle compound having at least four -A-CH 2 -CH 2 groups wherein A is a member selected from 0, OCH 2 S, SH 2 NR and NRCH 2 with R beit;g a member selected from hydrogen, alkyl and benzyl; and a hydrocarbon chain covalently bonded to said macrocyclic compound, with the hydrocarbon chain having an end group X °oca Si-0-Matrix in which X is selected from alkyl, benzyl, phenyl, X 0 8 X 00lo halogen, OCH 3 OC 2 H and 0-Matrix and Matrix is selected from glass, 9s" 3 2 5 glass fibers, titania, zirconia, alumina and nickel oxide. DATED this TWENTY-NINTH day of APRIL 1991 Brigham Young University *e 00 0 9000 Patent Attorneys for the Applicant SPRUSON FERGUSON *00 aB o LMM/KXW:1344y